Hydroboration of Nitriles, Esters, and Carbonates Catalyzed by Simple Earth-Abundant Metal Triflate Salts

Article abstract of DOI:10.1002/asia.202100003

During the past decade earth-abundant metals have become increasingly important in homogeneous catalysis. One of the reactions in which earth-abundant metals have found important applications is the hydroboration of unsaturated C?C and C?X bonds (X=O or N). Within these set of transformations, the hydroboration of challenging substrates such as nitriles, carbonates and esters still remain difficult and often relies on elaborate ligand designs and highly reactive catalysts (e. g., metal alkyls/hydrides). Here we report an effective methodology for the hydroboration of challenging C≡N and C=O bonds that is simple and applicable to a wide set of substrates. The methodology is based on using a manganese(II) triflate salt that, in combination with commercially available potassium tert-butoxide and pinacolborane, catalyzes the hydroboration of nitriles, carbonates, and esters at room temperature and with near quantitative yields in less than three hours. Additional studies demonstrated that other earth-abundant metal triflate salts can facilitate this reaction as well, which is further discussed in this report.

Full text of DOI:10.1002/asia.202100003

DOI: 10.1002/asia.202100003
Full Paper
Hydroboration of Nitriles, Esters, and Carbonates Catalyzed by
Simple Earth-Abundant Metal Triflate Salts
[a]
[a]
[b]
Ranjeesh Thenarukandiyil, Vanaparthi Satheesh, Linda J. W. Shimon, and
Graham de Ruiter*
[a]
Abstract: During the past decade earth-abundant metals
have become increasingly important in homogeneous catal-
ysis. One of the reactions in which earth-abundant metals
have found important applications is the hydroboration of
unsaturated CÀ C and CÀ X bonds (X=O or N). Within these
set of transformations, the hydroboration of challenging
substrates such as nitriles, carbonates and esters still remain
difficult and often relies on elaborate ligand designs and
highly reactive catalysts (e.g., metal alkyls/hydrides). Here we
report an effective methodology for the hydroboration of
challenging C�N and C=O bonds that is simple and
applicable to a wide set of substrates. The methodology is
based on using a manganese(II) triflate salt that, in combina-
tion with commercially available potassium tert-butoxide and
pinacolborane, catalyzes the hydroboration of nitriles, carbo-
nates, and esters at room temperature and with near
quantitative yields in less than three hours. Additional studies
demonstrated that other earth-abundant metal triflate salts
can facilitate this reaction as well, which is further discussed
in this report.
[15]
Introduction
ologies that utilize CO as an eco-friendly C feedstock. Because
2 1
of the stability of the C�N and C=O bond, both nitriles and
carbonate/esters are difficult substrates in the hydroboration
reaction. Only in the last few years has the hydroboration of
nitriles been more extensively explored with first-row transition
One of the most versatile synthetic tools in organic chemistry is
[1]
the hydroboration of unsaturated bonds. Typically catalyzed by
[2]
noble metals such as rhodium and iridium, the hydroboration
reaction provides useful synthons for the synthetic (organic)
[16]
metals. Trovitch and co-workers, for example, have reported a
[
3]
[4]
[17]
[18]
chemist. Beyond using noble metals, the use of earth-abundant
metals as catalyst has gained considerable attention during the
few cobalt and manganese complexes that are active for the
À 1 [17a]
dihydroboration of nitriles with TOFs of up to 380 h .
alkaline earth, second-row transition metals,
and other metals, have also been reported as catalyst for nitrile
hydroboration.
Akali or
actinides,
[5]
[19]
[13a,20]
[21]
past ten years. The low cost, wide availability, and reduced
toxicity associated with earth-abundant metal are important
incentives for transitioning to more sustainable chemical
processes. Indeed, the groups of Ritter, Lu, Chirik, Thomas,
and Huang and others, have made important contributions to
earth-abundant metal (Fe, Co, Ni, etc.) catalyzed hydroboration of
[22]
[23]
[6]
[7]
[8]
[9]
[10]
The hydroboration of carbonates or esters, on the other hand,
has less frequently been explored. Only a few examples have been
[11]
[12]
[
15a,24]
reported with magnesium-based catalysts,
while using other
[1b,c]
[25]
alkenes and alkynes.
earth-abundant metal based catalysts is scarce. To illustrate, just
recently Leitner and co-workers reported the first manganese
catalyst for the hydroboration of challenging carbonyl function-
In addition to the hydroboration of unsaturated
carbonÀ carbon bonds, the hydroboration of carbon–heteroatom
bonds (e.g., nitriles or carbonyls) is also of high interest. For
example, the hydroboration of nitriles provides synthetically useful
[
26]
alities such as carbonates and carbon dioxide. Although these
examples demonstrate that great progress has been made, the
hydroboration of nitriles and carbonate esters still requires long
reaction times (12–24 h), high temperatures (>80°C), and well-
defined catalyst often containing highly reactive metal alkyl/
[13]
borylamines and offers a mild and alternative reduction strategy
to the otherwise harsh conditions that are generally required for
[14]
catalytic nitrile hydrogenation. The hydroboration of carbonates
or esters on the other hand, is important for developing method-
[27]
hydride bonds. The aim of the herein presented study is to
remove the necessity for preparing and using these highly reactive
catalysts and to provide a simple and efficient methodology for
the hydroboration of challenging C�N and C=O bonds under
ambient conditions. Here we demonstrate that earth-abundant
metal triflate salts are able to efficiently catalyze the hydroboration
of nitriles, carbonates, and esters under ambient conditions
[a] Dr. R. Thenarukandiyil, Dr. V. Satheesh, Dr. G. de Ruiter
Schulich Faculty of Chemistry
Technion – Israel Institute of Technology
Technion City, 3200008 Haifa (Israel)
E-mail: graham@technion.ac.il
[
b] Dr. L. J. W. Shimon
(Figure 1). The reaction demonstrates a wide substrate scope and
Department of Chemical Research Support
Weizmann Institute of Science
Rehovot, 7610001 (Israel)
provides quantitative yields of most products in short reaction
times (%3 h).
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/asia.202100003
This manuscript is part of a special collection dedicated to Early Career
Researchers.
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[a,b]
Table 1. Catalyst screening for the dihydroboration of benzonitrile.
[
b]
Entry
Catalyst
Additive
EtMgBr
Yield [%]
1
2
3
4
5
6
7
8
9
0
1
2
3
[Mn(BDI)(OTf)
[Mn(BDI)(OTf)
Mn(OTf)
–
2
(CH
(CH
3
3
CN)]
CN)]
99
99
99
t
2
KO Bu
t
2
(CH
3
CN)
2
KO Bu
t
KO Bu
Trace
0
Mn(OTf)
2
(CH
3
CN)
2
–
t
MnCl
2
KO Bu
KO Bu
KO Bu
KO Bu
KO Bu
KO Bu
KO Bu
KO Bu
25
t
NaOTf
Mn(OTf)
Trace
t
[c]
2
(CH
3
CN)
2
99
t
Fe(OTf)
2
(CH
3
CN)
2
73
72
t
[c]
1
1
1
1
Fe(OTf)
2
(CH
3
CN)
2
t
Co(OTf)
Co(OTf)
2
(CH
(CH
3
CN)
CN)
2
74
71
t
[c]
2
3
2
t
Sc(OTf)
3
80
[
(
a] Reactions were performed with benzonitrile (0.5 mmol), HBpin
1.5 mmol, 3.00 equiv.), catalyst (3.0 mol%), with or without the presence
6
of an additive (9.0 mol%), in 0.5 mL of benzene-d for 3 h at RT. [b] Yields
1
were determined by H NMR spectroscopy in the presence of an internal
standard (mesitylene). [c] Reactions were performed in the presence of
mercury.
Figure 1. Herein presented hydroboration of nitriles (A), carbonates (B), and
esters (C) catalyzed by earth-abundant metal triflate salts.
version of benzonitrile to the N,N-diborylamine product in the
t
presence of KO Bu and HBpin (Table 1, entry 3). In the absence
Results and Discussion
of metal triflate salts, only trace amounts of product were
observed whereas without KO Bu no borylated products were
t
Our initial efforts for developing an efficient and simple
detected and only starting material was recovered (Table 1,
protocol for the hydroboration polar unsaturated CÀ X bonds
entries 4 and 5). Using other manganese salts (e.g., MnCl ), only
gave 25% of the desired borylamines (Table 1; entry 6). These
2
(
X=O or N) centered around exploring well-defined catalysts
containing redox non-innocent ligands and earth-abundant
metals. Realizing that earth-abundant metal complexes with
bipyridine (or phenanthroline) ligands are outstanding catalysts
experiments demonstrate the importance of the combination
t
Mn(OTf) , KO Bu, and HBpin for efficient hydroboration. Strik-
2
ingly, iron(II) and cobalt(II) triflate could also be used as catalyst,
albeit that the desired borylated products were obtained in
diminished yields (Table 1; entries 9 and 11). To rule out the
formation of heterogeneous particles of metallic Mn(0), Fe(0), or
Co(0), we performed the hydroboration of benzonitrile in the
presence of mercury (Table 1, entries, 8, 10, and 12). No
differences in yields were observed, advocating for a homoge-
neously catalyzed borylation pathway. Finally, to evaluate if
other transition metal-based Lewis acids are able to catalyze
nitrile hydroboration, we used commercially available scandium
[28]
in a variety of organic transformations, we based our initial
catalyst design on a manganese metal center that is supported
[29]
by an diimine functionalized bipyridine ligand (Figure S52).
Indeed, manganese complex [Mn(BDI)(OTf) (CH CN)] (1; BDI=
2
3
bipyridine-diimine) showed outstanding activity for the dihy-
droboration of benzonitrile (Table 1, entry 1 and 2). A combina-
tion of control experiments and optimization protocols, how-
ever, quickly established that metal(II) triflate salts of
manganese, iron, and cobalt are excellent catalysts for the
dihydroboration of benzonitrile (Table 1). Although earth-abun-
dant metal triflate salts have been used in a variety of organic
(III) triflate (Sc(OTf) ) as catalyst. As shown in Table 1 (entry 13),
3
Sc(OTf) provides the N,N-diborylamine product in reasonably
3
[30]
transformations, to the best of our knowledge, they have not
been used as catalyst for the hydroboration of nitriles or other
challenging carbonyl functionalities.
good yields (80%). The presence of other hidden catalyst such
as (Mg, Li, Al, Na) were ruled out by ICP analysis of the metal-
triflate salts (Table S6). Overall, these initial results suggest that
elaborate catalyst designs based on strong-field or redox non-
innocent ligands may not be necessary, and that earth-
abundant metal triflate salts are effective catalyst for nitrile
hydroboration.
The key for their catalytic activity is using a combination of
t
potassium tert-butoxide (KO Bu) and pinacolborane (HBpin),
which we originally intended to use as in-situ activator for
[31]
complex 1. Although other bases such as sodium methoxide
or ethoxide (NaOMe/NaOEt) could also be used, weaker bases
such as sodium acetate (NaOAc) or potassium carbonate
To further investigate this useful transformation, we used the
t
optimized reaction conditions: manganese triflate (3 mol%), KO Bu
(
K CO ) did not result in the desired reactivity of the metal
(9 mol%), and HBpin (3 equiv.) to hydroborate a diverse set of
aromatic and aliphatic nitriles (Table 2). For instance, changing
from benzonitrile to p-tolunitrile did not affect the yields, nor
2
3
[32]
triflate salt (Table S2). Notwithstanding, as evident from Table 1,
manganese(II) triflate showed excellent activity for the con-
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1000
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[
a–c]
Table 2. Substrate scope for the manganese(II) triflate catalyzed hydroboration of aromatic and aliphatic nitriles.
t
[
a] Reactions were performed with substrate (0.5 mmol), HBpin (1.5 mmol, 3.0 equiv.), Mn(OTf)
2
(CH
3 2
CN) (3.0 mol%), and KO Bu (9.0 mol%), in 0.5 mL of
1
benzene-d
6
for 3 h at RT. [b] Yields were determined by H NMR spectroscopy with mesitylene as internal standard. [c] For substrate 2j, 4 equiv. of HBPin were
used.
[1a,e]
changing the substitution pattern from para- to meta-tolunitrile
Table 2, 2b–2d). Only for o-tolunitrile a slight decrease in yield
hydroboration of ketones and aldehydes is well established,
did not pursue these substrate classes any further.
we
(
was observed, most likely due to the increased steric crowding
close to the nitrile functionality. Halogenated benzonitriles were
efficiently borylated as well, irrespective of the nature of the halide
Moving from aromatic to aliphatic nitriles generally did not
affect the hydroboration to a great extent. While for acetonitrile
diminished yields were observed (73%; 2o), other aliphatic nitriles
such as propionitrile and isobutyronitrile yielded their borylated
products in 97% and 98% respectively. Further increasing the alkyl
chain leads to near quantitative conversion as demonstrated for
octane- and dodecanenitrile. More structurally complex aliphatic
nitriles, such as 2-chlorohydrocinnamonitrile (2t), are efficiently
borylated as well. These results unequivocally demonstrate that
simple metal triflate salts are excellent catalysts for dihydrobora-
tion of various nitriles.
(e.g., F vs. Cl). Benzonitriles bearing electron withdrawing
substituents were efficiently borylated as well (Table 2, 2g).
Changing from electron poor to electron rich benzonitriles did not
have a marked effect on catalysis. Both 4-methoxy- and 3,4-
dimethoxybenzonitrile yielded the N,N-diborylamines in excellent
yields (>97%). Similarly, the presence of aromatic heterocycles
(i.e., 2m and 2n) did not result in diminished yields nor in
deactivation of the catalyst illustrating the broad substrate scope
of the herein presented catalytic system. Even the presence of
reducible functionalities such as alkenes did not affect the herein
reported borylation. For 4-ethynylbenzonitrile, however, reduced
yields (~60%) were observed accompanied with some side
product formation probably due to reduction of the alkyne
functionality (Figure S14). Other reducible functionalities (e.g.,
ketones) leads to the borylation of both the nitrile and the
carbonyl functional group within 3 hours (Table 2, 2j). Because the
To further demonstrate the applicability of the herein
reported methodology, we also investigated the hydroboration
of carbonates and esters. Only in the past three years, a few
earth-abundant metal complexes have been reported that
[15a,24–25,26]
facilitate the hydroboration of (carbonate) esters.
To
our delight, initial studies showed that almost all screened
metal(II) triflate salts were able to facilitate the borylation of
ethylene carbonate with near quantitative conversion (Fig-
ure 1B, Table S2). On other hand, for methyl benzoate only
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manganese(II) triflate showed excellent activity, while other
triflate salts only demonstrated poor activities (Figure 1C,
Table S2). Encouraged by these findings, we explored the scope
and limitations of the herein presented methodology with
various carbonates and esters (Table 3). Using catalytic con-
ditions that are similar to those employed for the hydroboration
of nitriles, excellent yields were obtained for the hydroboration
of cyclic carbonates such as ethylene, propylene, and trimeth-
ylene carbonate (Table 3, 3a–3c). Increasing the steric bulk of
the cyclic carbonate at the 2-position resulted in a significant
drop in yield of the borate ester (75%; 3d). Linear carbonates,
including aliphatic ones, are also efficiently hydroborated.
Normally these substrates require more stringent catalytic
conditions to facilitate their hydroboration, yet, with the herein
present protocol diethyl, dimethyl, and dibenzyl carbonate are
efficiently hydroborated (Table 3, 3e–3g). Asymmetrically sub-
stituent carbonates, including aromatic ones also provide the
corresponding borate esters in excellent yields (3h–3j).
Besides carbonates, various esters are also hydroborated
smoothly with manganese(II) triflate as catalyst (Table 3). With
manganese(II) triflate, almost all acetate esters (e.g. ethyl, benzyl,
hexyl, phenyl, tolyl etc.) are converted to their corresponding
borate esters in near quantitative yields (Table 3, 4b–4g). Only for
the sterically demanding tert-butyl acetate and tert-butyl propio-
nate moderate yields were observed (Table 3, 4h vs. 4i). Overall,
these results demonstrate that simple metal triflate salts (e.g., Mn)
[
a–c]
Table 3. Substrate scope for the manganese(II) triflate catalyzed hydroboration of carbonates and esters.
[
a] Reactions were performed with substrate (0.5 mmol), HBpin (1.5 mmol, 3.00 equiv. (1.6 mmol for carbonates)), Mn(OTf)
2
(CH
for 3 h at RT. [b] Yields were determined by H NMR spectroscopy with mesitylene as an internal standard. [c]
Only the main products of the hydroboration are shown; see the supporting information for more details.
3 2
CN) as catalyst (3.0 mol%),
t
1
and KO Bu (9.0 mol%), in 0.5 mL of benzene-d
6
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can efficiently catalyze the hydroboration of C�N and C=O bonds
in challenging substrates such as nitriles and carbonates.
applicable to a wide variety of substrates. Moreover, it does not
require any ligand preparation or formation of difficult to handle
metal hydride/alkyl species. The simplicity and generality of the
present method makes this a straightforward protocol in compar-
ison with most of the available hydroboration strategies for
challenging C�N and C=O functionalities. Current research is
directed towards expanding this methodology towards other
potential substrates such as carbamates and carboxamides which
remains challenging. Overall, we believe that the present study
will open up new research endeavors to use metal(II) triflate salts
as potential catalyst for various other organic transformations
including other hydrofunctionalization reactions.
[33]
Furthermore, the obtained boronates can subsequently be hydro-
lyzed and the corresponding amines and/or alcohols can be
obtained in good yields (Figure S56–S60). Additionally, the
reaction can also be performed in the absence of solvent where
near to quantitative results are obtained for representative
examples. (Figure S53–S55).
The mechanism for hydroboration of these types of
substrates frequently involves the in-situ formation of a metal
[27]
hydride species. Unfortunately, stoichiometric reactions with
t
HBpin, KO Bu or Mn(OTf) in benzene, toluene or THF resulted
2
in the formation complex reaction mixtures and attempts to
crystallize a putative metal-hydride species were unsuccessful.
1
1
In these experiments the B NMR spectrum showed the Experimental Section
t
formation of BuOBpin – or other (RO) B species – while GC-MS
3
primarily identified B Pin , which might indicate hydride transfer
General procedures
2
2
[31]
to a metal containing species (Figure S1–S3 and S61).
All reactions were performed at room temperature by using an N2-
filled glovebox unless otherwise specified. Glassware was oven
dried at 140°C for at least 2 h prior to use, and allowed to cool
under vacuum. All reagents were used as received unless
1
However, the H NMR spectrum of the reaction mixture did not
show any characteristic resonances in the hydride region
t
11
(
Figure S4). Besides BuOBpin, the B NMR in THF also showed
mentioned
otherwise.
Anhydrous
Mn(OTf) (MeCN) ,
Fe-
that (RO) BH is one of the major species along with several
2
2
3
(
OTf) (MeCN) and Co(OTf) (MeCN) were synthesized according to
2 2 2 2
[37]
other unidentifiable boron compounds (Figure S1–S3), which is
published procedures.
The pro-ligand; 1,1’-(2,2’-bipyridine-6,6’-
[31,34]
consisten with earlier studies by Thomas and Clark.
In the
diyl)bis(N-(2,4,6-trimethylphenyl)ethane-1-imine) (BDI) was synthe-
sized using a published procedure. MnCl , Fe (powder) and CoCl2
were purchased from Strem Chemicals, whereas Sc(OTf)3 was
purchased from Sigma Aldrich. The H spectra were recorded on
Bruker AVANCE III 400 MHz NMR spectrometer at room temperature
unless mentioned otherwise. All chemical shifts (δ) are reported in
ppm, and coupling constants (J) are in Hz. The H NMR spectra
were referenced using residual solvent peaks in the deuterated
absence of manganese triflate, (RO) BH remained one of the
[38]
3
2
À
major species although BH and BH were observed as well.
3
4
1
Both (RO) BH and BH have been shown to be catalytically
3
3
competent for the hydroboration of alkenes, alkynes, and
[
34–35]
ketones in the absence of metals.
Table 1), in the absence of metal triflate salt the hydroboration
of benzonitrile was minimal, ruling out that BH acts here as a
However, as evident from
1
(
3
solvent. Deuterated solvents, THF-d , benzene-d and toluene-d8
8
6,
[35]
hidden catalyst. The triflate counter ion was also eliminated
as potential catalyst, since sodium triflate failed to provide the
corresponding borylated products (Table 1, Entry 7 and Fig-
ure S5). Because (RO) BH – or other or other (RO) B species –
were purchased from Cambridge Isotope Laboratories, dried over
calcium hydride, degassed by three freeze-pump-thaw cycles and
vacuum-transferred prior to use.
3
3
were clearly present in the reaction mixture, we tentatively
propose that the earth-abundant metal triflate salts act as a
Lewis acid, activating the nitrile or carbonyl functionality
towards hydroboration with the in-situ generated boron “ate”
species according to the mechanism proposed by Clark (Fig-
Synthetic procedures
Synthesis of [Mn(BDI)(OTf) (CH CN)] (1). In the glovebox, a solution
2
3
of Mn(OTf) (CH CN) (434.0 mg, 1.00 mmol) in MeCN (5 mL) was
2
3
2
added – drop wise – to a stirred suspension of bipyridine-diimine
BDI ligand (474.0 mg, 1.00 mmol) in MeCN (50 mL). Upon addition
of the BDI ligand, the color of the reaction mixture gradually
changed to yellow while the suspension turned homogenous. The
homogenous solution was stirred for 16 h, where after the solvent
was removed under reduced pressure to yield a yellow solid. The
obtained solid was recrystallized by slow vapor diffusion of diethyl
ether into concentrated acetonitrile solution to yield the title
compound as yellow crystals. Yield 690 mg (79%). HRMS (TOF MS
[34]
ure S48). Recently a similar mechanism has been proposed by
Findlater and co-workers who demonstrated that a similar
boron “ate” species (i.e. Et BH) was competent for the hydro-
3
[
36]
boration of organic nitriles. However, despite these mecha-
nistic studies, the paramagnetism of the metal salts prevented a
detailed investigation, as such that other mechanisms that are
based on metal-hydrides cannot be exclusively excluded.
+
+
ES , positive ion; m/z): calcd. for [C33
H
5
F
6 2
N
O
4
SMn] : 678.1684;
34
3
3
found 678.1720. Anal. Calc. for C H F N O S Mn: C, 49.76; H, 4.29;
3
6
37
6
N, 8.06. Found: C, 49.20; H, 4.26; N, 7.89%.
Summary and Conclusions
General hydroboration procedures
In summary, we have demonstrated that simple earth-abundant
metal salts are excellent catalyst for the hydroboration of nitriles,
carbonates, and esters (>30 examples). The reaction occurs at
room temperature and provides the corresponding N,N-diboryl-
amines and borate esters in near quantitative yields within three
hours. The herein presented methodology is fast, efficient, and
Nitriles. In the nitrogen filled glovebox, pinacolborane (218 μL,
.5 mmol) was added to a vial containing a solution of Mn-
1
t
(
OTf) (CH CN) (6.5 mg, 3 mol%) and KO Bu (5 mg, 9 mol%) in
2 3 2
benzene-d (500 μL). The solution turned to pale brown immedi-
6
ately and the corresponding nitrile (0.5 mmol) was added. The
reactions were allowed to stir at room temperature for 3 h. Then a
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1
stock solution of mesitylene (87 μL; 720 mM in benzene-d ) was
2i; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 7.16-7.12 (m, 2H,
6 6
6
added and the reaction mixture was subsequently filtered through
a syringe filter. The yield of corresponding product was determined
by H-NMR-spectroscopy using mesitylene as internal standard.
ArÀ H), 6.68 (s, 1H, ArÀ H), 4.49 (s, À NCH ), 3.55 (s, 3H, À CH ), 3.47 (s,
2
3
3H, À CH ), 1.04 (s, 24H, À C(CH ) ). Spectroscopic data are in
3
3 2
1
[20a]
agreement with those previously reported.
1
Carbonates. In the nitrogen filled glovebox, pinacolborane (233 μL,
2j; Yield 97%. H NMR (400 MHz, C D ): δ (ppm) 7.53 (d, J=7.3 Hz,
6
6
.6 mmol) was added to a vial containing solution of Mn-
2H, ArÀ H), 7.39 ( d, J=7.4 Hz, 2H, ArÀ H), 5.46-5.40 (m, 1H,
t
OÀ CH(CH )), 4.56 (s, À CH ), 1.47 (d, J=4.2 Hz, 3H, À CH ), 1.03 (s,
2 3 2
3
2,
3
24H, À NBC(CH ) ), 0.99 (s, 12H, À OBC(CH ) ). Spectroscopic data are
6
3 2
3 2
[17a]
in agreement with those previously reported.
1
2
k; Yield 58%. H NMR (400 MHz, C D ): δ (ppm) 7.51 (d, J=8.2 Hz,
6
6
6
2
H, ArÀ H), 7.42 (d, J=8.1 Hz, 2H, ArÀ H), 4.51 (s, 2H, NCH ), 2.76(s,1H,
2
1
3
1
À CH),1.01 (s, 24H, À C(CH ) ). C { H} NMR (101 MHz, C D ): δ (ppm)
3
2
6
6
1
144.6, 132.3, 120.9, 84.3, 82.7, 77.3, 47.7, 24.7. HRMS (ESI, positive
+
ion): calcd. for [C H B NO ] : 384.2512; found: 384.2512
2
1
32
2
4
Esters. In the nitrogen filled glove box, pinacolborane (218 μL,
1
2
l: Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 7.55 (d, J=8.1 Hz,
6 6
1
.5 mmol) was added to a vial containing a solution of Mn-
t
2H, ArÀ H), 7.33 (d, J=8.1 Hz, 2H, ArÀ H), 6.64 (dd, J=17.6, 10.9 Hz,
(OTf) (CH CN) (6.5 mg, 3 mol%) and KO Bu (5 mg, 9 mol%) in
2 3 2
1
H,À CHÀ CH ), 5.63 (dd, J=17.6, 1.0 Hz, 1H„ -À CHÀ CH ), 5.07 (dd, J=
2
2
benzene-d (500 μL). The solution turned to pale brown immediately
6
1
0.9, 1.0 Hz, 1H, À CHÀ CH ), 4.61 (s, 2H, NCH ), 1.04 (s, 24H, À C(CH ) ).
2
2
3 2
and the corresponding ester (0.5 mmol) was added. The reactions
were allowed to stir at room temperature for 3 h. Then a stock
1
3
1
C { H} NMR (101 MHz, C D ): δ (ppm) 143.6, 137.4, 136.2, 126.5,
6
6
1
[
12.9, 82.6, 47.7, 24.7. HRMS (ESI, positive ion): calcd. for
C H B NO ] : 386.2668; found 386.2669.
solution of mesitylene (87 μL; 720 mM in benzene-d ) was added and
6
+
21 34 2 4
the reaction mixture was subsequently filtered through a syringe filter.
1
1
The yield of corresponding product was determined by H-NMR-
2
m; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 7.15–7.12 (m, 1H,
6 6
spectroscopy by using mesitylene as internal standard.
ArÀ H), 6.23–6.18 (m, 1H, ArÀ H), 6.17–6.12 (m, 1H, ArÀ H), 4.49 (s, 2H,
À NCH ), 1.03 (s, 24H, C(CH ) ). Spectroscopic data are in agreement
2
3 2
[17a]
with those previously reported.
Characterization data
1
2
n; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 7.07-7.02 (m, 1H,
6
6
1
2
2
4
a; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 7.51 (d, J=6 Hz,
6
6
ArÀ H), 6.95–6.89 (m, 1H, ArÀ H), 6.80–6.76 (m, 1H, ArÀ H), 4.61 (s, 2H,
H, ArÀ H), 7.21 (t, J=7.2 Hz, 2H, ArÀ H), 7.09 (t, J=7.6 Hz, 1H, ArÀ H),
À NCH ), 1.03 (s, 24H, À C(CH ) ). Spectroscopic data are in agreement
2
3 2
.51 (s, 2H, À CH ), 1.01 (s, 24H, C(CH ) ). Spectroscopic data are in
[16f]
2
3 2
with those previously reported.
[
17a]
agreement with those previously reported.
1
2
o; Yield 73%. H NMR (400 MHz, C D ): δ (ppm) 3.36 (q, J=6.8 Hz,
6
6
1
2
2
3
b; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 7.45 (d, J=6.5 Hz,
6
6
2H, NÀ CH ), 1.23 (t, J=6.9 Hz, 3H, À CH ), 1.05 (s, 24H, À C(CH ) ).
2
,
3
3 2
H, ArÀ H), 7.03 (d, J=6.5 Hz, 2H. ArÀ H), 4.50 (s, 2H, NCH ), 2.15 (s,
2
Spectroscopic data are in agreement with those previously
H, CH ), 1.02 (s, 24H, À C(CH ) ). Spectroscopic data are in agree-
[17a]
3
3 2
reported.
[
17a]
ment with those previously reported.
1
2
p; Yield 97%. H NMR (400 MHz, C D ): δ (ppm) 3.30(t, J=6.8 Hz,
6
6
1
2
c; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 7.33–6.93 (m, 4H,
6
6
2H, À NCH ), 1.66 (dd, J=13.6, 6.8 Hz, 2H, À NCH CH ), 1.04 (s, 24H,
2
2
2
ArÀ H), 4.50 (s, 2H, À NCH ), 2.17 (s, 3H, À CH ), 1.02 (s, 32H, À C(CH ) ;
2
3
3 2
À C(CH ) ), 0.88 (t, J=7.1 Hz, 3H, À CH ). Spectroscopic data are in
3
2
3
overlapping with HBpin resonances) Spectroscopic data are in
[17a]
agreement with those previously reported.
[
20a]
agreement with those previously reported.
1
2
q;Yield 98%. H NMR (400 MHz, C D ): δ (ppm) 3.17 (d, J=7.2 Hz,
6
6
1
2
d; Yield 88%. H NMR (400 MHz, C D ): δ (ppm) 7.53 (d, J=7.3 Hz,
6
6
2H, À NCH ), 1.96 (dp, J=13.5, 6.8 Hz, 1H, À CH(CH ) ), 1.04 (s, 24H,
2
3 2
1
H, ArÀ H), 7.19-7.16 (m, 1H, ArÀ H), 7.04 (t, J=6.8 Hz, 1H, ArÀ H), 6.96
C(CH ) ), 0.94 (d, J=6.7 Hz, 6H, À CH(CH ) ). Spectroscopic data are
3
2
3 2
(
3
d, J=6.9 Hz, ArÀ H), 4.49 (s, 2H, À NCH ), 2.11 (s, 3H, À CH ), 1.01 (s,
[17a]
2
3
in agreement with those previously reported.
3H, À C(CH ) ; overlapping with HBpin resonances). Spectroscopic
3
2
1
[16f]
2
r; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 3.29–3.34 (m, 2H,
data are in agreement with those previously reported.
6
6
NCH ), 1.69–1.58 (m, 2H, À CH ), 1.29–1.20 (m, 10H, À CH ), 1.04 (s,
2
2
2
1
2
e; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 7.40-7.34 (m, 2H,
6
6
24H, À C(CH ) ), 0.83 (t, J=8 Hz, 3H, À CH ). Spectroscopic data are in
3
2
3
ArÀ H), 6.89-6.82 (m, 2H, ArÀ H), 4.39 (s, 2H, À NCH ), 1.00 (s, 39H,
[20a]
2
agreement with those previously reported.
À C(CH ) ; overlapping with HBPin resonances). Spectroscopic data
3
2
1
[
17a]
2
(
s; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 3.32–3.25
are in agreement with those previously reported.
6
6
m,À NCH , 2H), 1.66–1.58 (m, 2H, À CH ), 1.29–1.16 (m, 18H, À CH ),
2
2
2
1
2
2
3
f; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 7.31 (d, J=7.1 Hz,
6
6
1.05 (s, 24H, C(CH ) ), 0.89–0.83 (m, 3H, À CH ). Spectroscopic data
3
2
3
H, ArÀ H), 7.16 (d, J=6.0 Hz, 2H, ArÀ H), 4.37 (s, 2H, À NCH ), 1.00 (s,
[20a]
2
are in agreement with those previously reported.
9H, À C(CH ) ; overlapping with HBpin resonances). Spectroscopic
3
2
1
[
16f]
2
t; Yield 98%. H NMR (400 MHz, C D ): δ (ppm) 7.21–7.15 (m, 1H,
data are in agreement with those previously reported.
6
6
ArÀ H), 7.05–6.98 (m, 1H, ArÀ H), 6.93–6.78 (m, 2H, ArÀ H), 3.42 (t, J=
1
2
g; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 7.4 (s(br), 4 H.
6
6
8 Hz, 2H, À NCH ), 2.82–2.75 (m, 2H, À CH ), 2.00–1.91(m, 2H, À CH ),
2
2
2
ArÀ H), 4.41 (s, 2H, À NCH ), 1.0 (s, 35H, À C(CH ) ; Overlapping with
2
3 2
1.05 (s, 24H, À C(CH ) ). Spectroscopic data are in agreement with
3
2
HBpin resonances). Spectroscopic data are in agreement with those
[20a]
those previously reported.
[17a]
previously reported.
1
3
a; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 3.88 (s, 4H, À OCH ),
6
6
2
1
2
2
3
h; Yield 97%. H NMR (400 MHz, C D ): δ (ppm) 7.48 (d, J=7.1 Hz,
6
6
3.47 (s, 3H, À OCH ), 1.07 (s, 24H, C(CH ) ), 1.04 (s, 12H, À C(CH ) for
3
3 2
3 2
H, ArÀ H), 6.82 (d, J=7.1 Hz, 2H, ArÀ H), 4.47 (s, 2H, À NCH ), 3.38 (s,
2
MeOBpin). Spectroscopic data are in agreement with those
H, À OMe), 1.03 (s, 24H, À C(CH ) ). Spectroscopic data are in
[26]
3
2
previously reported.
[
16f]
agreement with those previously reported.
Chem Asian J. 2021, 16, 999–1006
www.chemasianj.org
1004
© 2021 Wiley-VCH GmbH

Full Paper
1
3
b; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 4.45–4.37 (m, 1H,
products). Spectroscopic data are in agreement with those
previously reported.
6
6
[15a]
À OCH), 3.78 (d, J=4.1 Hz, 2H, OCH ), 3.47 (s, 3H, À OCH ), 1.08 (s,
2
3
2
4H, C(CH ) ), 1.04 (s, 12H, À C(CH ) for MeOBpin),1.03–1.00 (m, 3H,
3
2
3 2
1
4
f; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 6.99–6.92 (m, 2H,
6
6
À CHCH ). Spectroscopic data are in agreement with those pre-
3
[15a]
ArÀ H), 6.71 (t, J=7.8 Hz, 2H, ArÀ H), 3.88–3.81 (m, 2H, À OCH
2
), 1.12-
viously reported.
1
.06 (m, 15H, À C(CH ) for EtOBpin and –CH CH overlapping), 1.04
3
2
2
3
1
3
4
(
c; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 3.94 (t, J=5.5 Hz,
(s, 12H, À C(CH ) for F-PhOBPin). Spectroscopic data are in agree-
6
6
3 2
[15a,39]
H, À OCH ), 3.46 (s, 3H, À OCH ), 1.79–170 (m, 2H, À OCH CH ), 1.05
ment with those previously reported.
2
3
2
2
s, 36H, À C(CH ) , for both products). Spectroscopic data are in
3
2
1
[15a]
4g; Yield 99%. H NMR (400 MHz, C
D
6
): δ (ppm) 4.24–4.17 (m, 1H,
6
agreement with those previously reported.
À OCHÀ Cy), 3.9 (q, J=6.9 Hz, 2H, À OCH ), 1.92-1.85 (m, 2H,
2
1
3
3
1
d; Yield 75%. H NMR (400 MHz, C D ): δ (ppm) 3.96 (s, 4H, À OCH ),
À CH (Cy)), 1.64–1.56 (m, 2H, À CH (Cy)), 1.51–1.41 (m, 2H, À CH (Cy)),
6
6
2
2
2
2
.47 (s, 3H, À OCH ), 1.05 (s, 33H, C(CH ) (overlapping with HBpin)),
1.32–1.24 (m, 1H, À CH (Cy)), 1.20–1.13 (m, 3H, À CH (Cy)), 1.12–1.08
3
3 2
2
2
.02 (12H, C(CH ) for MeOBpin), 0.86 (s, 6H, À C(CH ) ). Spectro-
(m, 3H, À CH CH ) 1.07 (s, 12H, À C(CH ) for CyOBPin), 1.05 (s, 12H,
3
2
3 2
2
3
3 2,
[26]
scopic data are in agreement with those previously reported.
À C(CH ) for EtOBPin). Spectroscopic data are in agreement with
3
2,
[25d]
those previously reported.
1
3
1
e; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 3.46 (s, 3H, À OCH ),
6
6
3
1
.04 (s, 12H, À C(CH ) for MeOBpin). Spectroscopic data are in
4h; Yield 60%. H NMR (400 MHz, C D ): δ (ppm) 3.84 (q, J=6.9 Hz,
3
2
6
6
[
15a]
agreement with those previously reported.
2H), 1.33 (s, 9H,À C(CH ) ), 1.10–1.06 (m, 3H, À CH CH ) 1.05 (s, 12H,
3
3
2
3
t
À C(CH ) for BuOBPin), 1.05 (s, 12H, À C(CH ) of EtOBPin). Spectro-
1
3 2
3 2
3
2
1
f; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 3.84 (q, J=6.4 Hz,
[25d]
6
6
scopic data are in agreement with those previously reported.
H, À OCH ), 3.46 (s, 1.5 H, À OCH ), 1.09–1.06 (m, 3H, À CH À CH ),
2
3
2
3
1
.05 (s, 18H, À C(CH ) ; for both products). Spectroscopic data are in
4i; Yield 80%. H NMR (400 MHz, C D ): δ (ppm) 3.78 (t, J=6.4 Hz,
3
2
6
6
[
15a]
agreement with those previously reported.
2H, À OCH ), 1.52-1.44 (m, 2H, À CH À CH ), 1.31 (s, 9H, À C(CH ) ), 1.06
2
2
3
3 3
t
(
0
s, 12H, À C(CH ) for BuOBPin), 1.05 (s, 12H, À C(CH ) for PrOBPin),
1
3 2
3 2
3
2
(
g; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 7.27 (d, J=7.2 Hz,
6
6
.80 (t, J=7.3 Hz, 3H, À CH ). Spectroscopic data are in agreement
3
H, ArÀ H), 7.13 (t, J=7.1 Hz, 2H, ArÀ H), 7.06 (t, J=6.9 Hz, 1H), 4.90
[25d,26]
with those previously reported.
s, 2H, À OCH ), 3.48 (s, 1.5H, À OCH ), 1.04 (s, 18H, À C(CH ) ; for both
2
3
3 2
products). Spectroscopic data are in agreement with those
[15a]
previously reported.
1
Acknowledgements
3
7
7
4
h+3i; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 7.27 (d, J=
6
6
.0 Hz, 2H, ArÀ H), 7.18-7.11 (m, 4H, ArÀ H (for both products) 7.10–
.03 (m, 3H, ArÀ H (for both products)), 6.85 (t, J=6.1 Hz, 1H, ArÀ H),
Research was supported by the Azrieli Foundation (Israel). G.de.R
is an Azrieli young faculty fellow and a Horev Fellow supported by
the Taub Foundation. R.T. wishes to thank the Council for Higher
Education in Israel for an incoming PBC fellowship.
.90 (s, 2H, À OCH ), 3.48 (s, 3H, À OCH ), 1.05 (s, 36H, À C(CH ) ); for
2
3
3 2
three products). Spectroscopic data are in agreement with those
[
15a]
previously reported.
1
3
j+3k; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 3.84 (m, 2H,
6 6
À OCH ), 3.47 (s, 6H, À OCH ), 1.05 (s, 48 H, À C(CH ) for both
2
3
3 2
products overlapping with 3H, À CH À CH and HBpin). Spectroscopic
2
3
[
15a]
Conflict of Interest
data are in agreement with those previously reported.
1
4
a; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 7.27 (d, J=7.4 Hz,
6
6
The authors declare no conflict of interest.
2
H, ArÀ H), 7.13 (t, J=7.4 Hz, 2H, ArÀ H), 7.05 (t, J=7.3 Hz), 4.90 (s,
À OCH ), 3.47 (s, À OCH ), 1.04 (s, 24 H, À C(CH ) for both products).
2
3
3 2,
Spectroscopic data are in agreement with those previously
Keywords: Earth-Abundant Metals
Manganese · Nitriles · Carbonates and Esters
·
Hydroboration
·
[15a]
reported.
1
4
b; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 3.84 (q, J=7.0 Hz,
6 6
2
H, À OCH ), 1.09–1.05 (m, 3H, À CH CH ), 1.05 (s, 12 H, À C(CH ) ).
2
2
3
3 2
Spectroscopic data are in agreement with those previously
reported.
[15a]
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1
4
2
4
3
c; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 7.26 (d, J=7.5 Hz,
6 6
H, ArÀ H), 7.13 (t, J=7.4 Hz, 2H, ArÀ H), 7.05 (t, J=7.2 Hz, 1 H, ArÀ H),
.89 (s, 2H, À OCH ), 3.85(q, J=6.9 Hz, 2H, À OCH CH ), 1.10–1-06 (m,
2
2
3
H, À CH CH ), 1.05 (s, 12H, À C(CH ) for EtOBPin), 1.04 (s, 12H,
2
3
3 2
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3
2
2
[
15a]
with those previously reported.
1
4
d; Yield 99%. H NMR (400 MHz, C D ): δ (ppm) 7.09–7.02 (m, 2H,
6
6
ArÀ H), 6.88 (d, J=5.1 Hz, 2H, ArÀ H), 3.91-3.78 (m, 2H, À OCH ), 2.05
2
(
s, 3H, ArÀ CH ), 1.05 (s, 24H, À C(CH ) for both products).
3
3 2
Spectroscopic data are in agreement with those previously
[15a,39]
reported.
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4
e; Yield 97%. H NMR (400 MHz, C D ): δ (ppm) 7.05–6.92 (m, 3H,
6
6
ArÀ H), 6.68 (s, 1H, ArÀ H, overlapping with mesitylene), 3.91–3.78 (m,
2
H, À OCH ), 2.05 (s, 3H, -ArÀ CH ), 1.10–1.06 (m, 3H, À CH À CH
2
3
2
3,
overlapping with À C(CH ) ), 1.05 (s, 24H, À C(CH ) for both
3
2
3 2
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Manuscript received: January 1, 2021
Revised manuscript received: March 10, 2021
Accepted manuscript online: March 17, 2021
Version of record online: March 22, 2021
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